JP5102954B2 - Metal compound for laser marking and use thereof - Google Patents
Metal compound for laser marking and use thereof Download PDFInfo
- Publication number
- JP5102954B2 JP5102954B2 JP2005325283A JP2005325283A JP5102954B2 JP 5102954 B2 JP5102954 B2 JP 5102954B2 JP 2005325283 A JP2005325283 A JP 2005325283A JP 2005325283 A JP2005325283 A JP 2005325283A JP 5102954 B2 JP5102954 B2 JP 5102954B2
- Authority
- JP
- Japan
- Prior art keywords
- laser marking
- laser
- polyallylamine
- composition
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000010330 laser marking Methods 0.000 title claims description 85
- 150000002736 metal compounds Chemical class 0.000 title description 30
- 229920000083 poly(allylamine) Polymers 0.000 claims description 71
- 229920005989 resin Polymers 0.000 claims description 41
- 239000011347 resin Substances 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 150000004696 coordination complex Chemical class 0.000 claims description 17
- 229910010272 inorganic material Inorganic materials 0.000 claims description 16
- 239000011147 inorganic material Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 238000004040 coloring Methods 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 4
- 150000002815 nickel Chemical group 0.000 claims description 3
- 229910009372 YVO4 Inorganic materials 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- -1 inorganic acid salt Chemical class 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000003570 air Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- 150000004699 copper complex Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 229940078494 nickel acetate Drugs 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000638 stimulation Effects 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- 150000004700 cobalt complex Chemical class 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- 229940116318 copper carbonate Drugs 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007849 furan resin Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- AQIXEPGDORPWBJ-UHFFFAOYSA-N pentan-3-ol Chemical compound CCC(O)CC AQIXEPGDORPWBJ-UHFFFAOYSA-N 0.000 description 2
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- 239000010457 zeolite Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 241001561902 Chaetodon citrinellus Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
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- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SZOADBKOANDULT-UHFFFAOYSA-K antimonous acid Chemical compound O[Sb](O)O SZOADBKOANDULT-UHFFFAOYSA-K 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- UBFMILMLANTYEU-UHFFFAOYSA-H chromium(3+);oxalate Chemical compound [Cr+3].[Cr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UBFMILMLANTYEU-UHFFFAOYSA-H 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- GAYAMOAYBXKUII-UHFFFAOYSA-L cobalt(2+);dibenzoate Chemical compound [Co+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAYAMOAYBXKUII-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
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- 229910000431 copper oxide Inorganic materials 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 150000002367 halogens Chemical class 0.000 description 1
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- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
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- 150000004698 iron complex Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BUJJNPWRTNNUCG-UHFFFAOYSA-L iron(2+);dibenzoate Chemical compound [Fe+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 BUJJNPWRTNNUCG-UHFFFAOYSA-L 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011325 microbead Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- QNEIVTNMGMUAEX-UHFFFAOYSA-H oxalate rhodium(3+) Chemical compound [Rh+3].[Rh+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O QNEIVTNMGMUAEX-UHFFFAOYSA-H 0.000 description 1
- GKEBANQXMVUDHF-UHFFFAOYSA-H oxalate;ruthenium(3+) Chemical compound [Ru+3].[Ru+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O GKEBANQXMVUDHF-UHFFFAOYSA-H 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
Description
本発明は、レーザーマーキング用金属化合物、該レーザーマーキング用金属化合物を含有してなるレーザーマーキング用組成物、該レーザーマーキング用金属化合物の製造方法およびこれを用いた記録方法に関する。 The present invention relates to a metal compound for laser marking, a composition for laser marking comprising the metal compound for laser marking, a method for producing the metal compound for laser marking, and a recording method using the same.
近頃、電子部品、電気部品、電化製品、自動車部品、機械部品、シート、カード、フィルムなどの表面に製造年月日、製造会社名、製品名などを明記する方法として、非接触で且つマーキング速度が速く、幅広い素材の表面形状にとらわれることなくマーキング可能であり、自動化、工程管理が容易なことから、レーザーマーキングが普及している。また、レーザーマーキングは、素材自身に直接マーキングするため、インキ、溶剤および接着剤などを使わず済み、そのため環境的にもクリーンなマーキング方法として最近注目を受けている。 These days, non-contact and marking speed as a method of clearly specifying the date of manufacture, manufacturer name, product name, etc. on the surface of electronic parts, electrical parts, electrical appliances, automobile parts, machine parts, sheets, cards, films, etc. Laser marking is popular because it is fast, can be marked without being constrained by the surface shape of a wide range of materials, and is easy to automate and manage processes. In addition, since laser marking directly marks the material itself, it is not necessary to use inks, solvents, adhesives, etc., and therefore has recently received attention as an environmentally clean marking method.
現在、使用されているレーザーマーキングは、金属や樹脂などに直接レーザーを照射することにより、照射部分が熱分解したり蒸発することによって表面に物理的変化を生じさせたり、発色または脱色させることでマーキングする仕組みである。しかし、幅広い用途で使用されている樹脂製品をマーキングする場合、樹脂自身はレーザーの種類により多少の差はあるもののレーザー感度が低いためマーキングは容易ではない。特に、それらの樹脂は、大出力でありながら微細加工ができるＹＡＧレーザー光の波長１０６４ｎｍに対してはほとんど感度を持たない。
このような問題に対して、レーザー感度を持ちながら熱で変色する無機素材または有機素材を一緒に樹脂に添加し、樹脂成型物のレーザーマーキング性を向上させることが行われている（特許文献１〜３参照。）。
In order to solve such a problem, an inorganic material or an organic material that changes color with heat while having laser sensitivity is added to the resin together to improve the laser marking property of the resin molding (Patent Document 1). -3)).
しかし、上記方法により、レーザーマーキング時の発色性の問題は改善されるものの、上記方法による多くの素材は、鮮明な発色に必要なレーザーパワーまたは熱エネルギーが、媒体樹脂の分解温度と同程度、またはそれ以上である場合が多いため、レーザーマーキング時に媒体樹脂の発泡や分解を生じさせやすく、マーキングした基材または樹脂成形物の表面を凸凹に破壊すると言った問題を生じやすい。また、使用される多くの無機素材は、そのままでは粒子表面の親水性が高いため、樹脂との相溶性が悪く分散不良と言った問題も生じやすい。
そこで、本発明は、レーザーマーキングした基材または樹脂成形物表面を凸凹に破壊することなく、レーザー照射による光および熱刺激によりコントラストの高い黒色発色を示すレーザーマーキング用金属化合物、該レーザーマーキング用金属化合物を含有するレーザーマーキング用組成物、およびレーザー照射によりコントラストの高い黒色画像を記録する記録方法を提供することを目的とする。
However, although the problem of color developability at the time of laser marking is improved by the above method, many materials by the above method have the same laser power or thermal energy necessary for clear color development as the decomposition temperature of the medium resin, In many cases, it is more than that, and it is easy to cause foaming and decomposition of the medium resin at the time of laser marking, and the problem that the surface of the marked base material or the resin molding is broken unevenly tends to occur. Moreover, since many inorganic materials used have high hydrophilicity on the particle surface as they are, problems such as poor dispersion and poor dispersion are likely to occur.
Accordingly, the present invention provides a metal compound for laser marking that exhibits a high contrast black color by light and thermal stimulation by laser irradiation without destroying the laser-marked base material or resin molding surface unevenly, and the laser marking metal It is an object of the present invention to provide a composition for laser marking containing a compound and a recording method for recording a black image with high contrast by laser irradiation.
本発明は、ポリアリルアミン金属錯体および樹脂を含有することを特徴とするレーザーマーキング用組成物に関する。
また、前記金属が、銅またはニッケルであることを特徴とする上記レーザーマーキング用金属化合物が好ましい。
また、上記ポリアリルアミン金属錯体を構成する金属イオンのモル数に対するポリアリルアミン中のアミノ基のモル数のモル比が、０．２〜８．０であることが好ましい。
また、ポリアリルアミンが、１級アミンである上記レーザーマーキング用組成物が好ましい。
また、ポリアリルアミンの重量平均分子量が５００〜２０００００である上記レーザーマーキング用組成物が好ましい。
The present invention relates to a laser marking composition comprising a polyallylamine metal complex and a resin .
The metal is, the laser marking metal compound which is a copper or nickel is preferable.
The molar ratio of the number of moles of amino groups in the polyallylamine to the number of moles of metal ions constituting the polyallylamine metal complex is preferably 0.2 to 8.0.
Moreover, the said composition for laser marking whose polyallylamine is a primary amine is preferable.
Moreover, the said composition for laser marking whose weight average molecular weights of polyallylamine are 500-200000 is preferable.
次に、上記レーザーマーキング用組成物は、さらに、無機材料を含有することが好ましい。また、無機材料が、銅原子またはニッケル原子を含有することを特徴とする上記レーザーマーキング用組成物が好ましい。 Next, the upper Symbol laser marking composition preferably further contains an inorganic material. Moreover, the said composition for laser marking characterized by the inorganic material containing a copper atom or a nickel atom is preferable.
次に、本発明は、基材上に上記レーザーマーキング用組成物からなるレーザー発色層を有するレーザーマーキング用記録媒体に、レーザー照射により記録することを特徴とする記録方法に関する。
また、ＹＡＧレーザーまたはＹＶＯ４レーザーによってレーザー照射を行う上記の記録方法が好ましい。
Next, the present invention relates to a recording method comprising recording on a recording medium for laser marking having a laser coloring layer made of the above-described laser marking composition on a substrate by laser irradiation.
Further, the above recording method in which laser irradiation is performed with a YAG laser or a YVO4 laser is preferable.
本発明のレーザーマーキング用金属化合物および該レーザーマーキング用金属化合物を含有するレーザーマーキング用組成物は、高いレーザー感度を持ち、化学的にも物理的にも安定で、レーザーマーキング時に淡色から黒色または褐色に発色し、コントラストの高い画像を記録でき、優れたレーザーマーキング適性を示す。
また、本発明のレーザーマーキング用組成物を用いたレーザー照射による記録方法によれば、安定した濃度・色彩をもつコントラストの高い記録をすることができる。
The metal compound for laser marking of the present invention and the composition for laser marking containing the metal compound for laser marking have high laser sensitivity, are chemically and physically stable, and are light to black or brown at the time of laser marking. It is possible to record an image with high contrast and record high contrast, and exhibits excellent laser marking aptitude.
In addition, according to the recording method by laser irradiation using the laser marking composition of the present invention, it is possible to record with high density and stable contrast and color.
本発明のレーザーマーキング用金属化合物は、ポリアリルアミンと、該ポリアリルアミンと錯形成能を有する金属含有塩とを反応させて得ることができる化合物である。
また、前記レーザーマーキング用金属化合物、担持体、および必要に応じて無機材料を含有してなるレーザーマーキング用組成物も本発明の一態様である。
ここで、レーザーマーキングとは、レーザー照射による光刺激および発生する熱刺激などによって発色性や印字性を示す機能をいう。
The metal compound for laser marking of the present invention is a compound that can be obtained by reacting polyallylamine and a metal-containing salt having a complex-forming ability with the polyallylamine.
Moreover, the laser marking composition containing the metal compound for laser marking, a carrier, and, if necessary, an inorganic material is also an embodiment of the present invention.
Here, laser marking refers to a function that exhibits color developability and printability due to light stimulation by laser irradiation and generated thermal stimulation.
本発明のレーザーマーキング用金属化合物について説明する。前述の通り、レーザーマーキング用金属化合物は、ポリアリルアミンと、該ポリアリルアミンと錯形成能を有する金属含有塩とを反応させて得ることができるポリアリルアミン金属錯体である。
ポリアリルアミン金属錯体は、記録時の温度で分解反応または酸化反応を起こしやすく、非常に着色力の高い黒色または褐色に発色するものである。例えば、ポリアリルアミン銅錯体、ポリアリルアミンニッケル錯体、ポリアリルアミン鉄錯体、ポリアリルアミンコバルト錯体、ポリアリルアミンマンガン錯体、ポリアリルアミンクロム錯体、ポリアリルアミンルテニウム錯体、ポリアリルアミンロジウム錯体等が挙げられる。特に、ポリアリルアミン銅錯体、ポリアリルアミンニッケル錯体は、近赤外領域に高い吸収性を持つため、近赤外領域に波長を持つレーザーに対して感度が良好であり、記録時の発色性も高く好ましい。さらにこれらの材料は、疎水性を有するため、塗料などで使用される有機溶剤や担持体となる樹脂への相溶性が良好であるため加工性の面でも好ましい。また、製造面で安価であり好ましい。ポリアリルアミン金属錯体は、二種類以上を混合、または二種類以上の金属を合成時に複合化して用いてもよい。
The metal compound for laser marking of the present invention will be described. As described above, the metal compound for laser marking is a polyallylamine metal complex that can be obtained by reacting polyallylamine with a metal-containing salt having a complex-forming ability with the polyallylamine.
The polyallylamine metal complex easily undergoes a decomposition reaction or an oxidation reaction at the recording temperature, and develops a black or brown color with very high coloring power. For example, polyallylamine copper complex, polyallylamine nickel complex, polyallylamine iron complex, polyallylamine cobalt complex, polyallylamine manganese complex, polyallylamine chromium complex, polyallylamine ruthenium complex, polyallylamine rhodium complex and the like can be mentioned. In particular, polyallylamine copper complexes and polyallylamine nickel complexes have high absorbability in the near infrared region, so they have good sensitivity to lasers having wavelengths in the near infrared region and high color development during recording. preferable. Furthermore, since these materials have hydrophobicity, they have good compatibility with organic solvents used in paints and the like and resins used as carriers, and are also preferable in terms of workability. Moreover, it is inexpensive and preferable in terms of manufacturing. Two or more types of polyallylamine metal complexes may be mixed, or two or more types of metals may be combined during synthesis.
本発明のレーザーマーキング用金属化合物であるポリアリルアミン金属錯体を合成するために使用される錯形成能を有する金属含有塩は、無機酸塩でも有機酸塩でも良く、合成時に使用される媒体に溶解するものであれば特に限定するものではない。また、媒体への溶解性の観点から、金属含有塩の水和物を使用することも好ましい。例えば、硫酸銅、硫酸ニッケル、硫酸鉄（II）、硫酸鉄（III）、硫酸コバルト、硫酸マンガン、硫酸クロム、硫酸ルテニウム、硫酸ロジウム、硝酸銅、硝酸ニッケル、硝酸鉄（II）、硝酸鉄（III）、硝酸コバルト、硝酸マンガン、硝酸クロム、硝酸ルテニウム、硝酸ロジウム、塩化銅、塩化ニッケル、塩化鉄（II）、塩化鉄（III）、塩化コバルト、塩化マンガン、塩化クロム、塩化ルテニウム、塩化ロジウム、酢酸銅、酢酸ニッケル、酢酸鉄（II）、酢酸鉄（III）、酢酸コバルト、酢酸マンガン、酢酸クロム、酢酸ルテニウム、酢酸ロジウム、シュウ酸銅、シュウ酸ニッケル、シュウ酸鉄（II）、シュウ酸鉄（III）、シュウ酸コバルト、シュウ酸マンガン、シュウ酸クロム、シュウ酸ルテニウム、シュウ酸ロジウム、ステアリン酸銅、ステアリン酸ニッケル、ステアリン酸コバルトなどが挙げられる。特に、銅またはニッケルを含有する無機酸塩、及び有機酸塩は好ましい。さらに、硫酸銅、硫酸ニッケル、硝酸銅、硝酸ニッケルは、ポリアリルアミンと容易に反応し難溶性のポリアリルアミン金属錯体を得ることからより好ましい。 The metal-containing salt having the ability to form a complex used to synthesize the polyallylamine metal complex, which is the metal compound for laser marking of the present invention, may be an inorganic acid salt or an organic acid salt, and is dissolved in a medium used during the synthesis. If it does, it will not specifically limit. From the viewpoint of solubility in a medium, it is also preferable to use a hydrate of a metal-containing salt. For example, copper sulfate, nickel sulfate, iron (II) sulfate, iron (III) sulfate, cobalt sulfate, manganese sulfate, chromium sulfate, ruthenium sulfate, rhodium sulfate, copper nitrate, nickel nitrate, iron nitrate (II), iron nitrate ( III), cobalt nitrate, manganese nitrate, chromium nitrate, ruthenium nitrate, rhodium nitrate, copper chloride, nickel chloride, iron chloride (II), iron chloride (III), cobalt chloride, manganese chloride, chromium chloride, ruthenium chloride, rhodium chloride , Copper acetate, nickel acetate, iron acetate (II), iron acetate (III), cobalt acetate, manganese acetate, chromium acetate, ruthenium acetate, rhodium acetate, copper oxalate, nickel oxalate, iron (II) oxalate, sulphur Iron (III) oxalate, cobalt oxalate, manganese oxalate, chromium oxalate, ruthenium oxalate, rhodium oxalate, copper stearate, stearin Examples thereof include nickel acid and cobalt stearate. In particular, inorganic acid salts and organic acid salts containing copper or nickel are preferable. Furthermore, copper sulfate, nickel sulfate, copper nitrate, and nickel nitrate are more preferable because they easily react with polyallylamine to obtain a hardly soluble polyallylamine metal complex.
本発明のレーザーマーキング用金属化合物であるポリアリルアミン金属錯体を合成するために使用されるポリアリルアミンは、錯形成能を有する金属とアミノ錯体を形成するものであれば特に限定するものではない。特に、分子内に一級アミンを複数有するポリアリルアミンは、金属イオンとアミノ錯体を形成し易いことから好ましい。またこの一級アミンは、合成前に塩酸や酢酸などの酸と塩形成をしていることも可能である。さらに、ポリアリルアミンの重量平均分子量は、５００〜２０００００が好ましく、その範囲の中でも１０００〜１０００００がより好ましい。重量平均分子量が５００より小さい場合、得られたアミノ錯体が合成する際の媒体に対して溶解性が良好であるため収率が低くなり生産効率が悪い問題が生じ易い。また、重量平均分子量が２０００００より大きい場合、ポリアリルアミンの粘度が高くなることで合成溶液の粘度も高くなるため、高濃度での合成が難しくなり生産効率が悪い問題が生じ易い。ポリアリルアミンは、市販品でも使用可能であり、例えば、日東紡績製のＰＡＡ−０１、ＰＡＡ−０３、ＰＡＡ−０５、ＰＡＡ−０８、ＰＡＡ−１５、ＰＡＡ−１５Ｂ、ＰＡＡ−１０Ｃ、ＰＡＡ−２５、ＰＡＡ−Ｈ−１０Ｃ、ＰＡＡ−０３−Ｅ、ＰＡＡ-ＨＣｌ−０１、ＰＡＡ−ＨＣｌ−０３、ＰＡＡ−ＨＣｌ−０５、ＰＡＡ−ＨＣｌ−３Ｌ、ＰＡＡ−ＨＣｌ−１０Ｌ、ＰＡＡ-Ｈ-ＨＣｌ、ＰＡＡ−ＨＣｌ−３Ｓ、ＰＡＡ−ＨＣｌ−１０Ｓ、ＰＡＡ-ＳＡ、ＰＡＡ−Ｄ１１−ＨＣｌ、ＰＡＡ−Ｄ４１−ＨＣｌ、ＰＡＡ−Ｄ１９−ＨＣｌ、ＰＡＡ−Ｄ１９Ａ、ＰＡＡ−１１１２ＣＬ、ＰＡＡ−１１１２などが挙げられる。 The polyallylamine used for synthesizing the polyallylamine metal complex which is the metal compound for laser marking of the present invention is not particularly limited as long as it forms an amino complex with a metal having a complex forming ability. In particular, polyallylamine having a plurality of primary amines in the molecule is preferable because it easily forms an amino complex with a metal ion. Further, this primary amine can be salted with an acid such as hydrochloric acid or acetic acid before synthesis. Furthermore, the weight average molecular weight of polyallylamine is preferably 500 to 200,000, and more preferably 1000 to 100,000 in the range. When the weight average molecular weight is less than 500, the resulting amino complex has good solubility in the medium used for synthesis, and thus the yield is low and the production efficiency tends to be poor. On the other hand, when the weight average molecular weight is larger than 200,000, the viscosity of the polyallylamine is increased, so that the viscosity of the synthesis solution is also increased. The polyallylamine can also be used as a commercial product, for example, PAA-01, PAA-03, PAA-05, PAA-08, PAA-15, PAA-15B, PAA-10C, PAA-25 manufactured by Nitto Boseki, PAA-H-10C, PAA-03-E, PAA-HCl-01, PAA-HCl-03, PAA-HCl-05, PAA-HCl-3L, PAA-HCl-10L, PAA-H-HCl, PAA- HCl-3S, PAA-HCl-10S, PAA-SA, PAA-D11-HCl, PAA-D41-HCl, PAA-D19-HCl, PAA-D19A, PAA-1112CL, PAA-1112 and the like.
本発明のレーザーマーキング用金属化合物であるポリアリルアミン金属錯体を構成する錯形成能を有する金属イオンのモル数に対するポリアリルアミン中のアミノ基のモル数のモル比は、０．２〜８．０が好ましく、その範囲の中でも、０．５〜６．０がより好ましい。このモル比は、金属イオンの種類により異なるものである。例えば、銅イオンの場合０．５〜４．０、好ましくは０．５〜２．０、ニッケルイオンの場合０．８〜６．０、好ましくは１．０〜３．０、鉄イオンの場合１．０〜６．０、コバルトイオンの場合０．８〜６．０、マンガンイオンの場合１．０〜６．０、クロムイオンの場合１．０〜６．０などが挙げられる。特に、銅イオンの場合、モル比が０．５〜２．０の範囲内において近赤外吸収性の高いポリアリルアミン金属錯体を形成するため、近赤外領域に波長を持つレーザーに対して感度が良好となり、記録時の発色性もよく好ましい。具体的に、近赤外領域に波長を持つレーザーを用いる場合、使用するポリアリルアミン金属錯体自身の８００〜１２００ｎｍ範囲内の反射率は、７０％以下であることが好ましく、５０％以下であればより好ましい。さらに、使用するポリアリルアミン金属錯体の空気雰囲気下での熱分析測定における７００℃での残存重量比率としては、３５℃での重量を１００％とした際に１０％以上であることが好ましく、３０％以上であればより好ましい。 The molar ratio of the number of moles of amino groups in the polyallylamine to the number of moles of metal ions having a complex forming ability constituting the polyallylamine metal complex which is a metal compound for laser marking of the present invention is 0.2 to 8.0. Among these ranges, 0.5 to 6.0 is more preferable. This molar ratio varies depending on the type of metal ion. For example, in the case of copper ions, 0.5 to 4.0, preferably 0.5 to 2.0, in the case of nickel ions, 0.8 to 6.0, preferably 1.0 to 3.0, in the case of iron ions 1.0 to 6.0, 0.8 to 6.0 in the case of cobalt ion, 1.0 to 6.0 in the case of manganese ion, 1.0 to 6.0 in the case of chromium ion, and the like. In particular, in the case of copper ions, a polyallylamine metal complex having a high near-infrared absorptivity is formed within a molar ratio in the range of 0.5 to 2.0. And good color developability during recording. Specifically, when using a laser having a wavelength in the near-infrared region, the reflectance within the 800 to 1200 nm range of the polyallylamine metal complex itself used is preferably 70% or less, and if it is 50% or less. More preferred. Furthermore, the residual weight ratio at 700 ° C. in the thermal analysis measurement in the air atmosphere of the polyallylamine metal complex to be used is preferably 10% or more when the weight at 35 ° C. is 100%. % Or more is more preferable.
本発明のレーザーマーキング用金属化合物であるポリアリルアミン金属錯体を合成する際に使用可能な媒体としては、水または有機溶剤が挙げられる。有機溶剤の場合、水溶性の高いポリアリルアミンにあわせて水に対して相溶性のある溶剤が好ましい。具体的には、メタノール、エタノール、プロパノール、イソプロピルアルコール、１−ブタノール、２−ブタノール、１−ペンタノール、２−ペンタノール、３−ペンタノール、エチレングリコール、２−アミノエタノール、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、アセトニトリル、アセトン、メチルエチルケトン、１,４−ジオキサン、ジエチルエーテル、テトラヒドロフランなどが挙げられる。特に、メタノール、エタノール、アセトンは、錯形成能を有する金属含有塩の溶解性が良好であることから好ましい。 Examples of the medium that can be used when synthesizing the polyallylamine metal complex that is the metal compound for laser marking of the present invention include water and organic solvents. In the case of an organic solvent, a solvent compatible with water is preferred in accordance with polyallylamine having high water solubility. Specifically, methanol, ethanol, propanol, isopropyl alcohol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, ethylene glycol, 2-aminoethanol, N, N-dimethyl Examples include formamide, dimethyl sulfoxide, acetonitrile, acetone, methyl ethyl ketone, 1,4-dioxane, diethyl ether, and tetrahydrofuran. In particular, methanol, ethanol, and acetone are preferable because the solubility of the metal-containing salt having complex-forming ability is good.
本発明のレーザーマーキング用金属化合物の製造方法としては、上記構成原料や反応におけるモル比に従えば、特に限定されず、公知の方法を用いることができる。原料の添加方法に関しては、金属含有塩溶液にポリアリルアミンまたはその溶液を添加する方法や、ポリアリルアミン溶液に金属含有塩またはその溶液を添加する方法を用いることができる。特に、目的とする金属イオンのモル数に対するポリアリルアミン中のアミノ基のモル数のモル比を制御した均一なレーザーマーキング用金属化合物を得るためには、金属含有塩溶液にポリアリルアミンまたはその溶液を添加する方法が好ましい。さらに、合成後の乾燥温度に関しては特に限定するものではないが、加熱温度が高いほど、取り出したペースト中の含有水分や含有溶剤を除くことが可能となり、レーザーマーキング用金属化合物のレーザーに対する感度が増加するため好ましい。具体的には、３０〜１８０℃が好ましく、３５〜１５０℃がより好ましい。 The method for producing the metal compound for laser marking according to the present invention is not particularly limited as long as it follows the constituent raw materials and the molar ratio in the reaction, and a known method can be used. Regarding the method for adding the raw material, a method of adding polyallylamine or a solution thereof to a metal-containing salt solution, or a method of adding a metal-containing salt or a solution thereof to a polyallylamine solution can be used. In particular, in order to obtain a uniform metal compound for laser marking in which the molar ratio of the number of moles of amino groups in polyallylamine to the number of moles of the target metal ion is controlled, polyallylamine or a solution thereof is added to the metal-containing salt solution. The method of adding is preferable. Furthermore, the drying temperature after synthesis is not particularly limited. However, the higher the heating temperature, the higher the moisture content and solvent contained in the extracted paste can be removed. Since it increases, it is preferable. Specifically, 30-180 degreeC is preferable and 35-150 degreeC is more preferable.
次に、本発明のレーザーマーキング用組成物について説明する。
レーザーマーキング用組成物には、記録時の熱伝導性や、熱源となるレーザー光に対する感度を向上させるため、無機材料を含有させることが好ましい。無機材料は、二種類以上を混合して用いてもよい。また、レーザーマーキング用金属化合物と、一種以上の無機材料の混合重量比率は、９９．９：０．１〜１０：９０が好ましく、その範囲の中でも９５：５〜５０：５０がより好ましい。
Next, the composition for laser marking of the present invention will be described.
The composition for laser marking preferably contains an inorganic material in order to improve thermal conductivity during recording and sensitivity to laser light as a heat source. Two or more inorganic materials may be mixed and used. Moreover, 99.9: 0.1-10: 90 is preferable and, as for the mixing weight ratio of the metal compound for laser marking, and 1 or more types of inorganic material, 95: 5-50: 50 is more preferable in the range.
無機材料としては、金属の単体、塩、酸化物、水酸化物等を用いることができる。
金属の単体として具体的には、鉄、亜鉛、スズ、ニッケル、銅、銀、金等が挙げられる。
金属の塩として具体的には、炭酸カルシウム、炭酸銅、炭酸ニッケル、炭酸マンガン、炭酸コバルト、炭酸ランタン、硝酸マグネシウム、硝酸マンガン、硝酸鉄、硝酸カドミウム、硝酸亜鉛、硝酸コバルト、硝酸鉛、硝酸ニッケル、硝酸銅、硝酸パラジウム、硝酸ランタン、酢酸マグネシウム、酢酸マンガン、酢酸カドミウム、酢酸亜鉛、酢酸コバルト、酢酸鉛、酢酸ニッケル、酢酸銅、酢酸パラジウム、塩化銅、塩化鉄、塩化コバルト、塩化ニッケル、塩化銀、塩化亜鉛、リン酸銅、リン酸鉄、リン酸コバルト、ピロリン酸銅、硫酸銅、硫酸鉄、硫酸コバルト、シュウ酸銅、シュウ酸鉄、シュウ酸コバルト、安息香酸銅、安息香酸鉄、安息香酸コバルト等が挙げられる。
As the inorganic material, a simple metal, salt, oxide, hydroxide or the like can be used.
Specific examples of the simple metal include iron, zinc, tin, nickel, copper, silver, and gold.
Specific metal salts include calcium carbonate, copper carbonate, nickel carbonate, manganese carbonate, cobalt carbonate, lanthanum nitrate, magnesium nitrate, manganese nitrate, iron nitrate, cadmium nitrate, zinc nitrate, cobalt nitrate, lead nitrate, nickel nitrate , Copper nitrate, palladium nitrate, lanthanum nitrate, magnesium acetate, manganese acetate, cadmium acetate, zinc acetate, cobalt acetate, lead acetate, nickel acetate, copper acetate, palladium acetate, copper chloride, iron chloride, cobalt chloride, nickel chloride, chloride Silver, zinc chloride, copper phosphate, iron phosphate, cobalt phosphate, copper pyrophosphate, copper sulfate, iron sulfate, cobalt sulfate, copper oxalate, iron oxalate, cobalt oxalate, copper benzoate, iron benzoate, And cobalt benzoate.
金属の酸化物として具体的には、酸化ケイ素、酸化チタン、酸化アルミニウム、酸化鉄、酸化マグネシウム、酸化亜鉛、酸化コバルト、酸化鉛、酸化スズ、酸化アンチモン、酸化インジウム、酸化マンガン、酸化モリブテン、酸化ニッケル、酸化銅、酸化パラジウム、酸化ランタン、アンチモンドープ酸化スズ（ＡＴＯ）、インジウムドープ酸化スズ（ＩＴＯ）、合成ゼオライト、天然ゼオライト、銅−モリブテン複合酸化物等が挙げられる。金属酸化物としては、層状構造を有する、マイカ、モンモリロナイト、スメクタイト、タルク、クレー等を用いることもできる。 Specific examples of metal oxides include silicon oxide, titanium oxide, aluminum oxide, iron oxide, magnesium oxide, zinc oxide, cobalt oxide, lead oxide, tin oxide, antimony oxide, indium oxide, manganese oxide, molybdenum oxide, and oxide. Examples thereof include nickel, copper oxide, palladium oxide, lanthanum oxide, antimony-doped tin oxide (ATO), indium-doped tin oxide (ITO), synthetic zeolite, natural zeolite, and copper-molybten complex oxide. As the metal oxide, mica, montmorillonite, smectite, talc, clay and the like having a layered structure can also be used.
金属の水酸化物として具体的には、水酸化銅、水酸化アルミニウム、水酸化マグネシウム、水酸化亜鉛、水酸化アンチモン、水酸化コバルト、水酸化ニッケル、水酸化鉄、水酸化ランタン等が挙げられる。
特に、銅原子またはニッケル原子を含有する無機材料は、熱伝導性が良く、近赤外領域に吸収性を持ち、材料自身が感熱発色性を持つものが多いことからレーザーを用いた記録方法において、よりコントラストの高い画像の記録が得られるため好ましい。
Specific examples of the metal hydroxide include copper hydroxide, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, antimony hydroxide, cobalt hydroxide, nickel hydroxide, iron hydroxide, and lanthanum hydroxide. .
In particular, inorganic materials containing copper atoms or nickel atoms have good thermal conductivity, absorb in the near infrared region, and many materials themselves have thermochromic properties. It is preferable because an image with higher contrast can be recorded.
本発明のレーザーマーキング用組成物の構成成分となる担持体としては特に制限はないが、例えば熱硬化性樹脂、熱可塑性樹脂、光硬化性樹脂などの樹脂が挙げられる。これらの樹脂は単独で用いてもよく、２種類以上を混合して用いてもよい。
熱硬化性樹脂として具体的には、メラミン系樹脂、尿素系樹脂、フェノール系樹脂、エポキシ系樹脂、ウレタン系樹脂、ポリイミド系樹脂、ジアリルフタレート系樹脂、不飽和ポリエステル系樹脂、フラン系樹脂等が挙げられる。
Although there is no restriction | limiting in particular as a support body used as the structural component of the composition for laser markings of this invention, For example, resin, such as a thermosetting resin, a thermoplastic resin, a photocurable resin, is mentioned. These resins may be used alone or in combination of two or more.
Specific examples of thermosetting resins include melamine resins, urea resins, phenol resins, epoxy resins, urethane resins, polyimide resins, diallyl phthalate resins, unsaturated polyester resins, furan resins, and the like. Can be mentioned.
熱可塑性樹脂として具体的には、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリスチレン系樹脂、アクリル系樹脂、ポリ塩化ビニル系樹脂、ポリカーボネート系樹脂、ナイロン系樹脂、ウレタン系樹脂、ポリエステル系樹脂、ＡＢＳ系樹脂、ポリ乳酸系樹脂等が挙げられる。特に、燃焼時のダイオキシン類の発生原因となるハロゲンを含まず、安価で広く市場で使用されているポリプロピレン系樹脂、透明性が高く、リサイクル性の高いポリエステル系樹脂が好ましい。
光硬化性樹脂として具体的には、不飽和ポリエステル系樹脂、アクリレート系樹脂、ポリエン／ポリチオール系樹脂、スピラン系樹脂、エポキシ系樹脂、アミノアルキッド系樹脂、ジアリルフタレート系樹脂、不飽和ポリエステル系樹脂、フラン系樹脂等が挙げられる。
Specific examples of thermoplastic resins include polyethylene resins, polypropylene resins, polystyrene resins, acrylic resins, polyvinyl chloride resins, polycarbonate resins, nylon resins, urethane resins, polyester resins, ABS resins. And polylactic acid resin. In particular, a polypropylene resin that does not contain a halogen that causes generation of dioxins during combustion, is inexpensive and widely used in the market, and a polyester resin that is highly transparent and highly recyclable is preferable.
Specific examples of the photo-curable resin include unsaturated polyester resins, acrylate resins, polyene / polythiol resins, spirane resins, epoxy resins, aminoalkyd resins, diallyl phthalate resins, unsaturated polyester resins, Examples include furan resins.
レーザーマーキング用組成物を用いてレーザー発色層を形成する場合には、ポリビニルアルコールまたはその誘導体、ポリビニルブチラール、ポリビニルアセトアセタール等のポリビニルアセタール類、エチルセルロース、セルロースアセテート、セルロースアセテートプロピオネート、セルロースアセテートブチレート等のセルロース誘導体、エポキシ樹脂、アクリル系樹脂、ポリカーボネート系樹脂等の結着樹脂を担持体とすることが好ましい。結着樹脂は、二種類以上を混合して用いてもよい。 When a laser coloring layer is formed using a laser marking composition, polyvinyl alcohol or a derivative thereof, polyvinyl acetals such as polyvinyl butyral and polyvinyl acetoacetal, ethyl cellulose, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate It is preferable to use a binder resin such as a cellulose derivative such as a rate, an epoxy resin, an acrylic resin, or a polycarbonate resin as the carrier. Two or more kinds of binder resins may be mixed and used.
次に、レーザーマーキング用組成物を用いた記録方法について説明する。
記録は、レーザーマーキング用組成物を成型してなる成型物表面に、または基材上にレーザーマーキング用組成物からなるレーザー発色層を有する記録媒体に、レーザーにより記録することによって行う。
Next, a recording method using the laser marking composition will be described.
Recording is performed by recording with a laser on the surface of a molded product formed by molding the laser marking composition or on a recording medium having a laser color developing layer made of the laser marking composition on a substrate.
成型物表面にレーザー照射により記録する記録方法の場合には、成型物は、レーザーマーキング用金属化合物と熱可塑性樹脂とを含むレーザーマーキング用組成物を加熱成型することにより製造される。この場合、レーザーマーキング用組成物の全成分量に対して、レーザーマーキング用金属化合物の含有量は０.０５〜６０重量％が好ましく、０.５〜３０重量％がより好ましい。レーザーマーキング用金属化合物の含有量が６０重量％を超えると、熱可塑性樹脂の持つ柔軟性、成型性等の物性を損ねる可能性があるからである。また、白色でない少し着色がかったレーザーマーキング用金属化合物を使用する場合には、含有量を上げすぎると組成物全体の色調にも影響するため、含有量６０重量％以下の範囲内であることが好ましい。
成型物の製造に用いられるレーザーマーキング用組成物には、得られる成型物の記録特性を損なわない範囲で、酸化防止剤、滑剤、着色剤、帯電防止剤および防曇剤等を添加しても良い。
In the case of a recording method for recording on the surface of a molded product by laser irradiation, the molded product is produced by heat-molding a laser marking composition containing a metal compound for laser marking and a thermoplastic resin. In this case, the content of the metal compound for laser marking is preferably 0.05 to 60% by weight, and more preferably 0.5 to 30% by weight with respect to the total amount of components of the laser marking composition. This is because if the content of the metal compound for laser marking exceeds 60% by weight, physical properties such as flexibility and moldability of the thermoplastic resin may be impaired. In addition, when using a metal compound for laser marking that is slightly colored and not white, if the content is increased too much, the color tone of the entire composition is also affected, so the content may be within the range of 60% by weight or less. preferable.
An antioxidant, a lubricant, a colorant, an antistatic agent, an antifogging agent, etc. may be added to the composition for laser marking used in the production of a molded product as long as the recording characteristics of the obtained molded product are not impaired. good.
基材上にレーザー発色層を有するレーザーマーキング用記録媒体に、レーザー照射により記録するレーザーマーキング方法の場合には、レーザーマーキング用記録媒体は、レーザーマーキング用組成物を有機溶剤、水等からなる液状媒体に分散してなる塗工液を基材に塗工し、レーザー発色層を形成することにより製造される。この場合、塗工液の全成分量に対して、レーザーマーキング用金属化合物の含有量は０．５〜４０重量％であることが好ましく、２〜３０重量％であることがより好ましい。レーザーマーキング用金属化合物の含有量が４０重量％を超えると分散不良を起こしやすく、レーザーマーキング用記録媒体の感熱記録特性を損なう可能性があるからである。
塗工液には、塗工性の向上等を目的として、填料、界面活性剤、滑剤等を添加してもよい。
In the case of a laser marking method in which recording is performed by laser irradiation on a laser marking recording medium having a laser coloring layer on the substrate, the laser marking recording medium is a liquid comprising an organic solvent, water, or the like. It is manufactured by applying a coating liquid dispersed in a medium to a substrate to form a laser coloring layer. In this case, the content of the metal compound for laser marking is preferably 0.5 to 40% by weight and more preferably 2 to 30% by weight with respect to the total component amount of the coating liquid. This is because if the content of the metal compound for laser marking exceeds 40% by weight, poor dispersion tends to occur, and the thermal recording characteristics of the recording medium for laser marking may be impaired.
A filler, a surfactant, a lubricant and the like may be added to the coating liquid for the purpose of improving the coating property.
感熱記録組成物を有機溶剤、水等の液状媒体中に分散して塗工液を調製する際に使用する分散機としては、ペイントコンディショナー（レッドデビル社製）、ボールミル、サンドミル（シンマルエンタープライゼス社製「ダイノーミル」等）、アトライター、パールミル（アイリッヒ社製「ＤＣＰミル」等）、コボールミル、ホモミキサー、ホモジナイザー（エム・テクニック社製「クレアミックス」等）、湿式ジェットミル（ジーナス社製「ジーナスＰＹ」、ナノマイザー社製「ナノマイザー」）、微小ビーズミル（寿工業社製「ウルトラアペックミル」）等が挙げられる。分散機にメディアを使う場合には、ガラスビーズ、ジルコニアビーズ、アルミナビーズ、磁性ビーズ、スチレンビーズ等を用いることが好ましい。 Dispersers used when preparing a coating liquid by dispersing the heat-sensitive recording composition in a liquid medium such as an organic solvent or water include paint conditioners (manufactured by Red Devil), ball mills, sand mills (Shinmaru Enterprises). “Dynomill”, etc.), Attritor, Pearl Mill (“DCP Mill” manufactured by Eirich), Coball Mill, Homomixer, Homogenizer (“Claremix” manufactured by M Technique, etc.), Wet Jet Mill (“Genus” Genus PY ”,“ Nanomizer ”manufactured by Nanomizer Co., Ltd.), microbead mill (“ Ultra Apeck Mill ”manufactured by Kotobuki Kogyo Co., Ltd.) and the like. When using media in the disperser, it is preferable to use glass beads, zirconia beads, alumina beads, magnetic beads, styrene beads, or the like.
塗工液は、例えば、ワイヤーバーを用いて基材上に塗工することができる。
基材としては、紙、合成紙、プラスチックフィルム、金属箔、またはこれらの積層体が用いられる。
基材と感熱発色層との間には、発色性向上の目的からアンダーコート層を設けることも可能である。アンダーコート層は、アクリル系樹脂やスチレン系樹脂等で形成される球状樹脂微粒子や無機顔料等を結着樹脂に添加することにより構成される。
A coating liquid can be coated on a base material using a wire bar, for example.
As the substrate, paper, synthetic paper, plastic film, metal foil, or a laminate thereof is used.
An undercoat layer can be provided between the substrate and the heat-sensitive color developing layer for the purpose of improving color developability. The undercoat layer is configured by adding spherical resin fine particles, inorganic pigments, or the like formed of an acrylic resin, a styrene resin, or the like to the binder resin.
このようにして得られた成型物またはレーザーマーキング用記録媒体をレーザー照射することにより、照射部分のレーザーマーキング用金属化合物が熱により酸化分解または炭化し、素材によってはレーザーマーキング用金属化合物の周りに存在する樹脂等の担持体も熱により分解し変色することで、非常に鮮明なコントラストを持った記録を行うことができる。記録する際のエネルギー量は、レーザーマーキング用金属化合物の種類や量、記録部分の厚みなどによって異なるが、少なくともレーザーマーキング用金属化合物が酸化分解または炭化するためのエネルギー量は必要であり、記録時の発熱温度は１８０〜４５０℃であることが好ましく、２００〜３５０℃であることがより好ましい。 By irradiating the molded product or laser marking recording medium thus obtained with laser, the laser marking metal compound in the irradiated part is thermally decomposed or carbonized, and depending on the material, around the metal compound for laser marking. An existing carrier such as a resin is also decomposed and discolored by heat, so that recording with a very clear contrast can be performed. The amount of energy for recording varies depending on the type and amount of the metal compound for laser marking, the thickness of the recording part, etc., but at least the amount of energy required for oxidative decomposition or carbonization of the metal compound for laser marking is required. The exothermic temperature is preferably 180 to 450 ° C, more preferably 200 to 350 ° C.
レーザー照射により記録する場合、熱伝導率が高く、使用するレーザー光に対しても感度を有する無機材料を、本発明におけるレーザーマーキング用金属化合物と共に用いることが好ましい。レーザー光としては、例えばＹＡＧレーザー、ＹＶＯ４レーザー、グリーンレーザー、エキシマレーザー、炭酸ガスレーザー等が挙げられる。本発明で用いられるポリアリルアミン銅錯体またはポリアリルアミンニッケル錯体は、近赤外領域の光吸収性が高いため、よりコントラストの高い画像の記録ができるためには、近赤外領域に波長を持つＹＡＧレーザーやＹＶＯ４レーザーなどを用いることが好ましい。 In the case of recording by laser irradiation, it is preferable to use an inorganic material having high thermal conductivity and sensitivity to the laser beam used together with the metal compound for laser marking in the present invention. Examples of the laser light include a YAG laser, a YVO 4 laser, a green laser, an excimer laser, and a carbon dioxide gas laser. Since the polyallylamine copper complex or polyallylamine nickel complex used in the present invention has a high light absorption property in the near infrared region, a YAG having a wavelength in the near infrared region is necessary for recording a higher contrast image. It is preferable to use a laser, a YVO 4 laser, or the like.
また、本発明のレーザーマーキング用組成物を成型してなる成型物に対して、レーザー光を照射して記録をしながら、同時に加熱により樹脂成型物が溶融および固形化する機構を利用して、二つの樹脂成型物の間を融着させ繋げることもできる。 Further, for a molded product formed by molding the composition for laser marking of the present invention, using a mechanism in which a resin molded product is melted and solidified by heating while irradiating and recording a laser beam, It is also possible to fuse and connect the two resin moldings.
以下、実施例に基づき本発明をさらに詳しく説明するが、本発明は実施例に限定されるものではない。実施例中、部および％は、重量部および重量％をそれぞれ表す。 EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited to an Example. In the examples, parts and% represent parts by weight and% by weight, respectively.
（実施例１）ポリアリルアミン中のアミノ基のモル数／Ｃｕ２＋のモル数＝１．３における合成例
メタノール１０００部に、硫酸銅５水和物（和光純薬製）１００部を溶解させた。これに、ポリアリルアミン２０％水溶液（日東紡績製ＰＡＡ−０３：重量平均分子量３０００）１５０ｇとアセトン８５０ｇの混合溶液を１時間攪拌しながら滴下し、滴下後室温下で２時間攪拌した。析出物をろ過し、メタノール及びアセトンで洗浄を行い、３５℃で風乾させポリアリルアミン銅錯体（１）１２０部を得た。
(Example 1) Mole number of amino group in polyallylamine / Mole number of Cu 2+ = 1.3 Synthesis example 100 parts of copper sulfate pentahydrate (manufactured by Wako Pure Chemical Industries) was dissolved in 1000 parts of methanol. . To this, a mixed solution of 150 g of a polyallylamine 20% aqueous solution (PAA-03 manufactured by Nitto Boseki Co., Ltd .: weight average molecular weight 3000) and 850 g of acetone was added dropwise with stirring for 1 hour, and after the dropwise addition, the mixture was stirred at room temperature for 2 hours. The precipitate was filtered, washed with methanol and acetone, and air dried at 35 ° C. to obtain 120 parts of polyallylamine copper complex (1).
（実施例２）ポリアリルアミン中のアミノ基のモル数／Ｃｕ２＋のモル数＝０．８における合成例
メタノール１３００部に、硫酸銅５水和物（和光純薬製）１３１部を溶解させた。これに、ポリアリルアミン２０％水溶液（日東紡績製ＰＡＡ−０３：重量平均分子量３０００）１２０ｇとアセトン８６０ｇの混合溶液を１．５時間攪拌しながら滴下し、滴下後室温下で２時間攪拌した。析出物をろ過し、メタノール及びアセトンで洗浄を行い、３５℃で風乾させポリアリルアミン銅錯体（２）１３５部を得た。
(Example 2) Synthesis example in mole number of amino group in polyallylamine / number of moles of Cu 2+ = 0.8 In 131O parts of methanol, 131 parts of copper sulfate pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved. . To this, a mixed solution of 120 g of a polyallylamine 20% aqueous solution (PAA-03 manufactured by Nitto Boseki Co., Ltd .: weight average molecular weight 3000) and 860 g of acetone was added dropwise with stirring for 1.5 hours. After the addition, the mixture was stirred at room temperature for 2 hours. The precipitate was filtered, washed with methanol and acetone, and air dried at 35 ° C. to obtain 135 parts of a polyallylamine copper complex (2).
（実施例３）ポリアリルアミン中のアミノ基のモル数／Ｃｕ２＋のモル数＝３．５における合成例
メタノール１３００部に、硫酸銅５水和物（和光純薬製）１３１部を溶解させた。これに、ポリアリルアミン１５％水溶液（日東紡績製ＰＡＡ−１５：重量平均分子量１５０００）７００ｇとアセトン３０００ｇの混合溶液を２時間攪拌しながら滴下し、滴下後室温下で２時間攪拌した。析出物をろ過し、メタノール及びアセトンで洗浄を行い、３５℃で風乾させポリアリルアミン銅錯体（３）７５部を得た。
(Example 3) Mole number of amino group in polyallylamine / Mole number of Cu 2+ = 3.5 Synthesis example 131 parts of copper sulfate pentahydrate (manufactured by Wako Pure Chemical Industries) was dissolved in 1300 parts of methanol. . To this, a mixed solution of 700 g of a polyallylamine 15% aqueous solution (PAA-15 manufactured by Nitto Boseki Co., Ltd .: weight average molecular weight 15000) and 3000 g of acetone was added dropwise with stirring for 2 hours. After the addition, the mixture was stirred at room temperature for 2 hours. The precipitate was filtered, washed with methanol and acetone, and air dried at 35 ° C. to obtain 75 parts of polyallylamine copper complex (3).
（実施例４）ポリアリルアミン中のアミノ基のモル数／Ｎｉ２＋のモル数＝１．０における合成例
エタノール１３００部に、硝酸ニッケル６水和物（和光純薬製）１４３部を溶解させた。これに、ポリアリルアミン２０％水溶液（日東紡績製ＰＡＡ−０３：重量平均分子量３０００）１４０ｇとアセトン８６０ｇの混合溶液を１時間攪拌しながら滴下し、滴下後室温下で２時間攪拌した。析出物をろ過し、エタノール及びアセトンで洗浄を行い、３５℃で風乾させポリアリルアミンニッケル錯体（４）１００部を得た。
(Example 4) Synthesis example in mol number of amino group in polyallylamine / mol number of Ni 2+ = 1.0 In 1300 parts of ethanol, 143 parts of nickel nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved. . A mixed solution of 140 g of a polyallylamine 20% aqueous solution (PAA-03 manufactured by Nitto Boseki Co., Ltd .: weight average molecular weight 3000) and 860 g of acetone was added dropwise with stirring for 1 hour, and after the dropwise addition, the mixture was stirred at room temperature for 2 hours. The precipitate was filtered, washed with ethanol and acetone, and air dried at 35 ° C. to obtain 100 parts of a polyallylamine nickel complex (4).
（実施例５）ポリアリルアミン中のアミノ基のモル数／Ｎｉ２＋のモル数＝４．０における合成例
エタノール１３００部に、硝酸ニッケル６水和物（和光純薬製）１４３部を溶解させた。これに、ポリアリルアミン１５％水溶液（日東紡績製ＰＡＡ−０８：重量平均分子量８０００）７４０ｇとアセトン３０００ｇの混合溶液を２時間攪拌しながら滴下し、滴下後室温下で２時間攪拌した。析出物をろ過し、エタノール及びアセトンで洗浄を行い、３５℃で風乾させポリアリルアミンニッケル錯体（５）１４０部を得た。
(Example 5) Synthesis example in mol number of amino group in polyallylamine / mol number of Ni 2+ = 4.0 In 1300 parts of ethanol, 143 parts of nickel nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved. . A mixed solution of 740 g of a polyallylamine 15% aqueous solution (PAA-08 manufactured by Nitto Boseki Co., Ltd .: weight average molecular weight 8000) and 3000 g of acetone was added dropwise with stirring for 2 hours. After the addition, the mixture was stirred at room temperature for 2 hours. The precipitate was filtered, washed with ethanol and acetone, and air dried at 35 ° C. to obtain 140 parts of a polyallylamine nickel complex (5).
（実施例６）ポリアリルアミン中のアミノ基のモル数／Ｃｏ２＋のモル数＝２．０における合成例
エタノール１０００部に、硝酸コバルト６水和物（和光純薬製）７１．４部を溶解させた。これに、ポリアリルアミン２０％水溶液（日東紡績製ＰＡＡ−０３：重量平均分子量３０００）１４０ｇとアセトン１０００ｇの混合溶液を１時間攪拌しながら滴下し、滴下後室温下で２時間攪拌した。析出物をろ過し、エタノール及びアセトンで洗浄を行い、３５℃で風乾させポリアリルアミンコバルト錯体（６）３５部を得た。
(Example 6) Synthesis example in mol number of amino group in polyallylamine / mol number of Co 2+ = 2.0 In 1.4 parts of ethanol, 71.4 parts of cobalt nitrate hexahydrate (manufactured by Wako Pure Chemical Industries) was dissolved. I let you. A mixed solution of 140 g of polyallylamine 20% aqueous solution (PAA-03 manufactured by Nitto Boseki Co., Ltd .: weight average molecular weight 3000) and 1000 g of acetone was added dropwise thereto with stirring for 1 hour. The precipitate was filtered, washed with ethanol and acetone, and air dried at 35 ° C. to obtain 35 parts of a polyallylamine cobalt complex (6).
（実施例７〜１６）成型物の作成
・マスターバッチの作成方法
表１に示すポリプロピレン系樹脂８０部と、表１に示す添加剤［合成例で得られたポリアリルアミン金属錯体単独またはポリアリルアミン金属錯体と無機材料の混合品（混合重量比率８０：２０）］２０部とを溶融混練機にて混練することにより、ペレット状の樹脂組成物（マスターバッチ）を得た。無機材料は、炭酸銅（東罐マテリアルテクノロジー製）、酢酸ニッケル（和光純薬製）、酸化チタン（石原産業製「Ｒ−８３０」）、ＡＴＯ（石原産業製「ＳＮ−１００Ｐ」）を用いた。
・フィルム成型方法
得られたマスターバッチ５０部と、マスターバッチの作成に用いたのと同様のポリプロピレン系樹脂５０部とを混合し、２２０℃で溶融押出し、厚さ２００μｍのレーザーマーキング用記録フィルムを得た。これらを順に実施例７〜１６とした。
(Examples 7 to 16) Preparation of molded article / Master batch production method 80 parts of polypropylene resin shown in Table 1 and additive shown in Table 1 [polyallylamine metal complex alone or polyallylamine metal obtained in Synthesis Example] A pellet-shaped resin composition (masterbatch) was obtained by kneading 20 parts of a complex-inorganic material mixture (mixing weight ratio 80:20)] with a melt kneader. As the inorganic material, copper carbonate (manufactured by Toago Material Technology), nickel acetate (manufactured by Wako Pure Chemical Industries), titanium oxide (manufactured by Ishihara Sangyo “R-830”), ATO (manufactured by Ishihara Sangyo “SN-100P”) were used. .
-Film molding method 50 parts of the obtained master batch and 50 parts of the same polypropylene resin used for the production of the master batch are mixed, melt-extruded at 220 ° C, and a laser marking recording film having a thickness of 200 µm is obtained. Obtained. These were made into Examples 7-16 in order.
（実施例１７〜２６）レーザーマーキング用記録媒体の作成
メチルエチルケトン５０部、表２に示す添加剤［合成例で得られたポリアリルアミン金属錯体単独またはポリアリルアミン金属錯体と無機材料の混合品（混合重量比率８０：２０）］３０部、ウレタン樹脂２０部をサンドミルで混合分散したあと、その分散液に更にウレタン樹脂１０部を添加し塗工液を調製した。坪量４０ｇ／ｍ2の原紙に、得られた塗工液をワイヤーバーで塗工量（固形分）６ｇ／ｍ２となるように塗工し、乾燥した後スーパーカレンダーで加圧処理してレーザーマーキング用記録媒体を得た。これらを順に実施例１７〜２６とした。
(Examples 17 to 26) Preparation of recording medium for laser marking 50 parts of methyl ethyl ketone, additive shown in Table 2 [Polyallylamine metal complex obtained in Synthesis Example alone or a mixture of polyallylamine metal complex and inorganic material (mixed weight) (Ratio 80:20)] After 30 parts of urethane resin and 20 parts of urethane resin were mixed and dispersed by a sand mill, 10 parts of urethane resin was further added to the dispersion to prepare a coating solution. Apply the obtained coating solution to a base paper with a basis weight of 40 g / m 2 with a wire bar so that the coating amount (solid content) is 6 g / m 2, and after drying, pressurize with a super calender. A recording medium for laser marking was obtained. These were made into Examples 17-26 in order.
（記録方法）
得られたレーザーマーキング用記録フィルム（成型物）およびレーザーマーキング用記録媒体について、ＹＶＯ４レーザー「ＹＶＯ社製ｉ-Ｍａｒｋｅｒ１０Ｗ」（連続描画）を使用してレーザー照射を行い、記録画像の反射濃度（Ｏ．Ｄ.値）をマクベス濃度計で測定した。レーザーマーキング用記録フィルム（成型物）に記録した結果を表１に、レーザーマーキング用記録媒体に記録した結果を表２に示す。
(Recording method)
The obtained laser marking recording film (molded product) and laser marking recording medium are irradiated with laser using a YVO 4 laser “Y-Marker 10W” (continuous drawing), and the reflection density of the recorded image ( OD value) was measured with a Macbeth densitometer. The results recorded on the laser marking recording film (molded product) are shown in Table 1, and the results recorded on the laser marking recording medium are shown in Table 2.
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